Dyestuffs of the anthraquinone series and a process of making same



Patented Dec. 17, 1946 a 1 UNITED s'r TEs PATENT OFFICE nynsrnrrs OF snares AND A SAME THE ANTHRAQUINONE PaocEssoF MAKING Samuel von Allmen and Hans Eggenberger, Basel,

' Switzerland, assignors to Switzerland No Drawing! Applicatio N0. 541,283. In Swi The present invention relates to new dyestuffs of the anthraquinone series possessing an improved stability to artificial light and to a proc ess for their preparation.

It is known that the dyestufis of the anthraquinone series containing in their molecule the radical of an aromatic amine corresponding to the general formula.

-hal.

wherein hal. stands for bromine or chlorine,

possess a much redder shade than the correspond ing isomers containing the halogen in p-position to the amino group. The m-substituted compounds are known as being valuable violet acid dyestuifs (of. U. S. Patent No. 1,898,861, Example 6).

It is further known that group corresponding to the the dyestuffs of the general formula X NH:

0 .SO@H

. H H I wherein one of the X represents a. sulphonic acid group, the other X being hydrogen, give reddish-blue shades which change to red in artificial light (of. U. S. Patent No. 1,898,861, Ex-

. ample 6) It has now been found that the dyestuffs corresponding to the general formula,

0 NHz t Y s0n1 i NQ wherein one of the Y/stands for a sulphonic acid group, the other Y being hydrogen and wherein X stands for a substituent selected from the group consisting of halogen, COOH, alkyl, COO OH, OR,R meaning an alkyl group, possess unexpected fastness to artificial light, so that thesame are very suitable for vdyeing and printing animal fibres.

The process for the manufacture of these. new.

. 4 chloranthraquinone-Zzfiwhich can be used,

- the condensation the Sandoz Ltd., Fribourg,

11 Jane 20, 1944, Serial tzeriand uly 16, 1943 7 Claims. (Cl. 260372) dyestufis consists in condensing, in an aqueous or organic solvent or in a mixture thereof at temperatures between 50 and 150 0., a l-amino- 2:4-dihalogenanthraquinone-6- or -7-sulphonlc acid with a meta-substituted aniline corresponding to the general formula wherein X stands for a substituent selected from the group consisting of halogen, COOH, alkyl,

tained with sulphites in order to substitute the halogen atom by a sulphonic acid group.

The same dyestuffscan also be prepared by condensing l-amino 4 halogenanthraquinone- 2:6- or -2:7-disulphonic acid with a meta-substituted aniline under the above-described condensation conditions. 7 As amines used for the manufacture of the new dyestufis may be cited for instance metatoluidine, meta-chloraniline, meta-bromaniline, meta aminobenzoic acid,

As sulphonated aminohalogenanthraquinones come into consideration, for example, 1 amino-2z4-dibromanthraquinone-6- or -7-sulph0nic acid, 1-amino-2:4-dichloranthra- 6- or -7-sulphonic acid, 1-amino-4-bromanthraquinone-2:6- or -2:7-disulphonic acids, l-aminoor 2:7 disulphom'c acids, or mixtures of theisomers.

-The present invention will now be illustrated, but not limited by the following examples, whereare heated under stirring during 12 hours at During the interaction the shade of the reaction mass changes monosulphonated dyestuff.

meta ethy1aniline,- meta-aminobenzoic acid methyl ester, metaaminophenol, meta-anisidine.

from red to blue. After is separated and heated with a solution of a sulphite, until the halogen atom has been replaced by a sulphonic acid group. The disulq phonated dyestuff is then isolated in the usual way.

The new dyestnfi dyes wool, silk, hairs, leather and synthetical fibres, like nylon, in beautiful blue shades which do not change in artificial light.

The new dyestufi can also be prepared by; condensing l-aminoAbromanthraquinone2:6- disulphonic acid with meta-toluidine. Its isomeric compound containing the sulphonic acid groups in 2:7-positlons has a similar shade.

The same dyestuil can also be prepared by starting from 1-amino-4-chloranthraquinone- 2 6- or -2 fl-disulphonic acids.

hours at 80 C.

is heated together during After. the condensation, the. monosulphonated dyestufi is isolated and Example 1,

The new disulphonated dyestufi dyes animal fibres in blue-reddish shades, which remain un-: changed in artificial. light.

Example 3 treated. as described in;

- A mixture consisting of:

. Parts: l-aminol-brornanthrai's heated for several hours at 80" C. Therea'ctionmass is then poured into new dyestnff separated according to, theusual methods.

It dyes animal fibres in-blue-reddish shades which do not change to red, when exposedto artificial light;

Example 4 5.6 parts of meta-aminobenzoic; acidareadisa solved at C. in 6.0.partsoirwater and neudilutedacidjand' the" Example 2- A. mixture consisting of: Parts Potassium salt of. 1-am-ino-2zl-dibromam thraquinone-l-sulphonic acid 10 Meta-chloraniline 3.9 Sodium bicarbonate 4.8 Copper powder 0.2 Water Ethanol N 20 tralized with 3.2 partsof sodiummarbonatez. To;

this solution are added of l amino 224 dibromanthraquinone-7-sulphonic acid, 0.2 part of copper powder and 10 parts of water, and the mixture is heated for 4 hours at 80 C. and a further hour at 95 C. After. the condensation the mono-sulphonated dyestuff is separated and treated with a hot solution of a sulphite in the manner. describedin Example 1. I

i The disulphonated dyestufi thusobtained dyes animal fibres in beautiful blue-reddish shades, which remain unchanged in artificial light.

Example 5v 10; parts o p t Salt;-

To this solution are added 13 parts of the sddium. salt of 1,amino-4rchloranthraquinone-2 :6- disulphonic acid and 0.2: part of: copper; powder, and the mixture is heated under stirring at 80 C., until the condensation has finished.

The new dyestuff thus obtained dyes animal fibres in blue-reddish shades, which remain unchanged in' artificial light.

Example 6 wherein one Y stands for. a sulphonic acid group, the other Y being hydrogen, and wherein X stands for a substituent, consisting of halogen, alkyl; COOHCQOF-alKyl; OH'and' Q-alkyL, which. dyestuffs .dye animal and related fibres blue shadeswhich are un: changedwhen exposed to. artificial light.

2. The new dyestufi of the-formula NHz dyeing animal and related fibres in blue shades which are unchanged when exposed to artificial light.

- 3. The: new dyestuff of the formula} shades which are unchanged when-exposed to ar- 5.6 parts-of meta-aminobenzolc. acid: are. dis

solved in parts :of water and neutralizedwidah:

3zzip'arts. of 'sodium carbonate.

tificial light. I

4. The new dyestuff of the formula Hooch;

dyeing.;-..anirna1t and -"rielated fibresz'inabluezshtides selected from: the, group which are unchanged when exposed to artificial light.

5. A process for the manufacture of new dyestufis of the anthraquinone series comprising the step of condensing an anthraquinone derivative of the general formula (I? NH: 0 x 503K I! O halogen wherein halogen stands, for a member of the group consisting of chlorine and bromine and wherein one X is a sulpho group, the other); being hydrogen, with an amine of the general formula the step of condensing the anthraqui'none coinpound of the formula 2% l SO:H

with m-aminobenzoic acidmethylester in an aqueous medium in presence of copper as catalyst and of an acid binding agent.

'7. The process for the manufacture of a new dyestufi of the anthraquinone series comprising the step of condensing the anthraquinone compound of the formula with m-toluidine in an aqueous medium in presence of copper as catalyst and of an acid binding agent.

SAMUEL VON ALLMEN. HANS EGGENBERGER.

Certificate of Correction Patent No. 2,412,790

SAMUEL VON ALLMEN ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 2, line 35, for 4-dichloranthraread 4-dichl0mnthraquinone-; column 4 last formula, left-hand portion thereof, for

11035-- read H0] and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 20th day of December, A. D. 1949.

THOMAS F. MURPHY,

Assistant Oammz'm'oner of Patents.

December 17, 1946 

